CN111082054B - Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof - Google Patents
Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of lithium-sulfur battery materials, and particularly discloses a lithium-sulfur battery positive electrode material which comprises a positive electrode active material, a conductive agent and a binder, wherein the positive electrode active material has a structural formula
Wherein R is1、R2Independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl, heterocycloaryl, ether or tertiary amino; the value of x is an integer of 1-20. The compound with the structure is innovatively adopted as the positive active material of the lithium-sulfur battery, a 2.55-2.65V discharge platform is provided based on a carbon-sulfur double-bond lithium storage mechanism in the charging and discharging processes, and the voltage of the discharge platform is much higher than that of two discharge platforms (2.2-2.3V and 1.9-2.1V) of the traditional lithium-sulfur battery, so that the energy density of the battery is greatly improved.
Description
Technical Field
The invention relates to a sulfur-containing organic matter cathode material and a lithium-sulfur battery assembled by the same, belonging to the field of lithium secondary batteries.
Background
With the development of society, on one hand, the performance requirements of the public on portable electronic products are continuously improved; on the other hand, people have increased environmental awareness and knowledge of non-renewable resources, so that energy storage power stations, electric vehicles and smart power grids of various scales begin to develop rapidly. The two reasons are that the requirements on the energy density and the power density of the lithium ion battery are higher and higher, but the lithium ion battery system with the best comprehensive performance at present is difficult to meet the requirements on high specific energy in the future society due to the limitation of the theoretical lithium storage capacity of the battery system and the electrode material.
Lithium-sulfur batteries are the most promising alternatives to lithium-ion batteries because their theoretical energy density (2500Wh/kg) is much higher than the energy density of existing lithium ions (200 Wh/kg). However, it is undeniable that there are many problems to be solved in the Li-S battery, one of which is that the electronic conductivity and ionic conductivity of elemental sulfur are poor, and the conductivity of sulfur material at room temperature is very low (5.0 × 10)-30S·cm-1) End product of the reaction Li2S2And Li2S is also an electronic insulator, which is not conducive to high rate performance of the battery; secondly, intermediate discharge products of the lithium-sulfur battery can be dissolved in the organic electrolyte, the viscosity of the electrolyte is increased, the ionic conductivity is reduced, polysulfide ions can migrate between a positive electrode and a negative electrode, and a shuttle effect is generated, so that active substances are lost and electric energy is wasted. Thirdly, the lithium-sulfur battery uses metal lithium as a negative electrode, and the metal lithium negative electrode has volume change and is easy to form dendrite in the charging and discharging process except for the high activity of the metal lithium itself. For the reasons mentioned above, the actual stable gram capacity of sulfur (600-900 mAh/g) is much lower than the theoretical gram capacity (1675 mAh/g). Therefore, the actual energy density of the lithium-sulfur secondary battery successfully developed at present is far lower than the theoretical energy density (about 300-500 Wh/kg), the cycle life is short, and the actual use requirement is far from being met. In order to increase the actual gram capacity of sulfur and thus the actual specific energy, researchers have devised a number of strategies. For example, a nano-structure carbon material with a high specific surface area is adopted, sulfur is adsorbed in pores of the carbon material, and polysulfide shuttling is prevented through physical adsorption and limiting effects, so that the loss of active sulfur is reduced, for example, patent CN201410256653 discloses a nitrogen-doped graphene coated nano-sulfur positive electrode composite material, nano-sulfur particles are uniformly coated by a nitrogen-doped graphene sheet layer, so that the dissolution and shuttling effects of polysulfide in a lithium sulfur battery are effectively inhibited, and the specific discharge capacity of the battery is improved.CN201611218937 prepares a battery interlayer with strong adsorption capacity by compounding an ultralight carbonized bacterial cellulose interlayer with porous carbon, prepares a battery diaphragm material by combining an ion selective barrier layer Nafion and a bacterial cellulose aerogel, controls polysulfide diffusion to a lithium cathode in a multi-layer manner by introducing a functional interlayer and using a Nafion/BC diaphragm in a combined manner, realizes multi-stage inhibition on polysulfide diffusion, and improves specific capacity of the battery. The above methods all improve the gram capacity of the positive active material to some extent, but based on the charge-discharge mechanism of dissolution-deposition of the lithium-sulfur battery itself, a part of the positive active material inevitably needs to be dissolved and lost in the electrolyte to form polysulfide conductive lithium ions, so that the gram capacity of sulfur itself has a limit lower than the theoretical value.
Disclosure of Invention
Aiming at the technical problem of low actual specific energy of the existing lithium-sulfur battery, the invention aims to provide a lithium-sulfur battery cathode material with a high-voltage discharge platform.
The second purpose of the invention is to provide a lithium-sulfur battery positive electrode containing the positive electrode material.
A third object of the present invention is to provide a lithium-sulfur battery loaded with the positive electrode.
A positive electrode material for a lithium-sulfur battery includes a positive electrode active material, a conductive agent, and a binder;
the positive active material has a structural formula of formula 1:
R1、R2independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl, heterocycloaryl, ether or tertiary amino;
x is an integer of 1-20.
The compound with the structural formula 1 is innovatively used as the positive active material of the lithium-sulfur battery, and a carbon-sulfur double bond lithium storage mechanism in the compound and the polysulfide characteristic are utilized, so that a 2.55-2.65V discharge platform is realized in the charge-discharge process, and the discharge platform is far higher than two discharge platform voltages (2.2-2.3V and 1.9-2.1V) of the traditional lithium-sulfur battery. The compound with the structure shown in the formula 1 is used as the positive electrode material of the lithium-sulfur battery, so that the energy density of the battery is greatly improved.
In the invention, the structural characteristics of-C ═ S and Sx in the molecular structure of the positive electrode active material are the key points for endowing the material with a high discharge platform; further research shows that R is controlled1、R2And x, the electrical properties of the positive active material can be further improved.
Preferably, the positive active material is at least one of compounds with structural formulas of formula 1-A and formula 1-B;
wherein R is3～R6Independently C1-C6 alkyl, C2-C6 alkenyl or alkynyl or C6-C12 aryl; or, R3～R6In (C) to (R)3And R4Cyclization; r5And R6Ring closure) to form a five-to six-membered saturated, partially unsaturated or fully unsaturated cyclic group containing N.
Preferably, the ring-forming carbons of the cyclic group also allow hybridization by heteroatoms, preferably nitrogen atoms.
Further preferably, R is3～R6Independently C1-C6 alkyl. Or, R3、R4Cyclizing to form six-membered piperidyl, pyrimidyl or pyridyl. R5、R6Cyclizing to form six-membered piperidyl, pyrimidyl or pyridyl.
Preferably, R7、R8Independently C1-C6 alkyl or C6-C12 aryl.
The inventor researches and finds that the electrical property of the positive electrode active material, preferably represented by formula 1-A, is better, and particularly, the electrical property is better when the number of the substituent carbon is less.
Preferably, the value of x is an integer between 1 and 8.
The R1 and the R2 are independently selected from the same or different.
Preferably, the particle diameter of the positive electrode active material is 1nm to 150 μm, and more preferably 1 to 20 μm.
Preferably, the conductive agent is one or more of graphene, conductive carbon black, ketjen black, acetylene black and carbon nanotubes. The particle size of the conductive agent is preferably 1nm to 20 μm.
Preferably, the binder is one or more of polyvinylidene fluoride (PVDF), styrene butadiene rubber, polyethylene oxide (PEO).
Preferably, the binder average molecular weight (Mv) is preferably 60w to 800 w.
The compound represented by formula 1 is a positive electrode active material and is a main component of the positive electrode material.
Preferably, in the positive electrode material, the positive electrode active material is contained in an amount of 60 to 85% by mass.
The dosage and proportion of the conductive agent and the binder can be adjusted according to the requirement.
More preferably, the positive electrode material comprises a positive electrode active material, a conductive agent and a binder, and the mass ratio is preferably (60-85) to (10-30) to (5-10).
The invention also provides a lithium-sulfur battery positive electrode, which comprises a positive electrode current collector and the positive electrode material compounded on the surface of the positive electrode current collector.
The invention also provides a preparation method of the lithium-sulfur battery positive electrode, which comprises the following steps:
(1) mixing the positive electrode active material and the conductive agent uniformly (for example, mechanically grinding by a physical method);
(2) adding the binder into the dispersion solvent and stirring to form a solution;
(3) adding the dry material ground and premixed uniformly in the step one into the solution in the step two, and stirring or super-mixing
Acoustically dispersing to form a slurry;
(4) and coating the slurry on a current collector, and drying at high temperature to remove the solvent to obtain the lithium-sulfur battery anode.
According to the positive electrode, the positive active material and the conductive agent are mixed in advance through ball milling by the preparation method; and then mixed with the solution containing the binder, which helps to overcome the problems of excessive and uneven dispersion of active material particles during the preparation of the material, and helps to prepare a positive electrode of a lithium-sulfur battery having excellent electrical properties.
The dispersing solvent can be a component known to those skilled in the art, preferably NMP.
The invention also provides a lithium-sulfur battery assembled by the sulfur-containing positive electrode provided by the invention.
The lithium-sulfur battery comprises the positive electrode (positive plate), the negative electrode (negative plate), a diaphragm for separating the positive electrode and the negative electrode, and electrolyte for soaking the positive electrode and the negative electrode.
Preferably, the diaphragm is positioned between the positive plate and the negative plate, and the positive plate, the negative plate, the diaphragm and the electrolyte are sealed in the battery shell package.
The negative plate is a metal lithium or lithium boron alloy negative electrode.
The electrolyte includes a solvent, a lithium salt, and an additive. The solvent is one or a mixture of more of DOL, DME, PEGDME, DMSO, MiPS, EMS, TMS, FEC, EC and DMC; the lithium salt is LiTFSI, LiFSI, LiDFOB, LiDFBOP, LiBOB, LiBETI or LiPF6、LiBF4、LiAsF6、LiClO4One or more of the above; the additive is LiNO3、NH4TFSI、LiI、AlI3、P2S5One or more of VC and EDOT.
The technical scheme of the invention has the following beneficial effects:
the organic sulfur-containing active material provided by the invention is simple in preparation process and easy to process, a 2.55-2.65V discharge platform is provided based on a carbon-sulfur double-bond lithium storage mechanism in the charging and discharging processes, and the voltage of the discharge platform is much higher than that of two discharge platforms (2.2-2.3V and 1.9-2.1V) of the traditional lithium-sulfur battery, so that the energy density of the battery is greatly improved.
Drawings
FIG. 1 is a graph showing the charge and discharge current density of 50mA g in the positive electrode material of example 1 of the present invention-1。
FIG. 2 is a graph showing the charge and discharge curves of elemental sulfur powder according to comparative example 1 of the present invention, wherein the charge and discharge current density is 50mA g-1。
FIG. 3 is a graph showing the charge and discharge current density of 100mA g of the positive electrode material in example 1 of the present invention-1。
Fig. 4 is a cyclic voltammogram of the cathode material of example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
The positive active material adopted in the case has the structural formula
Adding 0.06g of acetylene black serving as a conductive agent and 0.03g of polyvinylidene fluoride serving as an adhesive into 0.21g of finely ground positive active material, uniformly mixing the materials, putting the mixture into 1.8g N-methyl pyrrolidone, uniformly stirring the mixture, coating the mixture on copper foil, putting the copper foil into an oven with the temperature of 80 ℃ for drying, punching the mixture into a pole piece by using a punch with the diameter of 13mm, tabletting the pole piece under the pressure of 1MPa, putting the pole piece into a vacuum oven with the temperature of 100 ℃ for drying for 4 hours to obtain a positive pole piece, transferring the positive pole piece into an argon glove box, taking a metal lithium piece as a negative pole, selecting a polypropylene microporous membrane with the model of Celgard 2400 as a diaphragm, and using 1.0M of electrolyte LiTFSI DOL and DME (V: V) +0.2M of LiNO as3And assembling into a CR2025 battery, standing in a thermostatic chamber at 25 ℃ for 12h, and then carrying out electrical performance test. The results of the charge and discharge tests are shown in fig. 1, and the discharge voltage plateau can be increased to 2.6V as compared with the test results (fig. 2) of the battery in comparative example 1. The current density of the charge and discharge is tested to be 50 mA.g-1And discharge capacity of 842mAh gs -1. FIG. 3 shows the charge/discharge current density of 100mA g-1The discharge capacity was 756mAh gs -1. The cyclic voltammetry curve is shown in fig. 4, and the oxidation-reduction peak potential is consistent with the charge-discharge platform voltage.
Example 2
The positive active material adopted in the case has the structural formula
Adding 0.06g of acetylene black serving as a conductive agent and 0.03g of polyvinylidene fluoride serving as an adhesive into 0.21g of finely ground positive active material, uniformly mixing the materials, putting the mixture into 1.8g N-methyl pyrrolidone, uniformly stirring the mixture, coating the mixture on copper foil, putting the copper foil into an oven with the temperature of 80 ℃ for drying, punching the mixture into a pole piece by using a punch with the diameter of 13mm, tabletting the pole piece under the pressure of 1MPa, putting the pole piece into a vacuum oven with the temperature of 100 ℃ for drying for 4 hours to obtain a positive pole piece, transferring the positive pole piece into an argon glove box, taking a metal lithium piece as a negative pole, selecting a polypropylene microporous membrane with the model of Celgard 2400 as a diaphragm, and using 1.0M of electrolyte LiTFSI DOL and DME (V: V) +0.2M of LiNO as3And assembling into a CR2025 battery, standing in a thermostatic chamber at 25 ℃ for 12h, and then carrying out electrical performance test. The three voltage platforms are respectively 2.55V, 2.2V and 2.1V, and the tested charging and discharging current density is 100 mA-g-1And a discharge capacity of 928mAh gs -1。
Example 3
The positive active material adopted in the case has the structural formula
Adding 0.06g of acetylene black serving as a conductive agent and 0.03g of polyvinylidene fluoride serving as a bonding agent into 0.21g of ground positive electrode active material, uniformly mixing, putting into 1.8g N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, putting into an oven with the temperature of 80 ℃ for drying, punching into a pole piece by using a punch with the diameter of 13mm, tabletting under the pressure of 1MPa, and putting into a vacuum oven with the temperature of 100 ℃ for drying for 4 hours to obtain a positive electrodeTransferring the sheet into an argon glove box, taking a metal lithium sheet as a negative electrode, selecting a polypropylene microporous membrane of Celgard 2400 as a diaphragm, and selecting 1.0M LiTFSI DOL and DME as electrolyte, namely 1:1 (V: V) +0.2M LiNO3And assembling into a CR2025 battery, standing in a thermostatic chamber at 25 ℃ for 12h, and then carrying out electrical performance test. The voltage platform is 2.55V, and the tested charging and discharging current density is 50mA g-1The discharge capacity was 796mAh · gs -1。
Example 4
The positive active material adopted in the case has the structural formula
Adding 0.06g of acetylene black serving as a conductive agent and 0.03g of polyvinylidene fluoride serving as a bonding agent into 0.21g of ground active material, uniformly mixing, putting the mixture into 1.8g N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, putting the copper foil into an oven with the temperature of 80 ℃ for drying, punching the mixture into a pole piece by using a punch with the diameter of 13mm, tabletting the pole piece under the pressure of 1MPa, putting the pole piece into a vacuum oven with the temperature of 100 ℃ for drying for 4 hours to obtain a positive pole piece, transferring the positive pole piece into an argon glove box, taking a metal lithium piece as a negative pole, selecting a polypropylene microporous membrane with the model of Celgard 2400 as a diaphragm, and using 1.0M LiTFSI DOL of electrolyte and 1:1 (V: V) +0.2M LiNO of electrolyte3And assembling into a CR2025 battery, standing in a thermostatic chamber at 25 ℃ for 12h, and then carrying out electrical performance test. The voltage platform is 2.6V, and the tested charging and discharging current density is 50mA g-1Discharge capacity of 821mAh gs -1。
Comparative example 1
Preparing slurry by the elemental sulfur powder, the acetylene black and the polyvinylidene fluoride according to the ratio of 7: 2: 1, coating the slurry on the carbon-coated aluminum foil, and drying the carbon-coated aluminum foil in an oven at 80 ℃ for 8 hours until NMP is completely volatilized. And punching the dried sulfur pole piece into a round pole piece with the diameter of 13mm, and drying in an oven at the temperature of 55 ℃ for 1 hour. In argon atmosphere, a metal lithium sheet is taken as a negative electrode, a polypropylene microporous membrane with the model of Celgard 2400 is selected as a diaphragm, and 1.0M LiTFSI DOL and DME of electrolyte are 1:1 (V: V) +0.2M LiNO3And assembling the button cell. The discharge capacity is 887mAh/g, and the discharge voltage platforms are respectively 2.2V and 2.05V.
Claims (7)
1. A positive electrode material for a lithium-sulfur battery, comprising a positive electrode active material, a conductive agent and a binder, characterized in that: the positive active material is a compound with a structural formula of 1-B;
1-B
R7、R8independently is C1~C6Alkyl or C6~C12An aromatic group of (a);
x is an integer between 1 and 8;
the conductive agent is acetylene black;
the binder is polyvinylidene fluoride;
the mass ratio of the positive electrode active material to the conductive agent to the binder is (60-85): (10-30): (5-10).
2. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the particle size of the conductive agent is 1nm to 20 μm.
3. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the binder has an average molecular weight of 60w to 800 w.
4. A lithium sulfur battery positive electrode, characterized in that: the positive electrode material comprises a positive electrode current collector and the positive electrode material as claimed in any one of claims 1 to 3 compounded on the surface of the positive electrode current collector.
5. A method for preparing the positive electrode of the lithium-sulfur battery according to claim 4, comprising
The following steps:
(1) uniformly mixing the positive active material with a conductive agent;
(2) adding the binder into the dispersion solvent and stirring to form a solution;
(3) adding the dry materials ground and premixed uniformly in the step (1) into the solution in the step (2), and stirring or super-mixing
Acoustically dispersing to form a slurry;
(4) and coating the slurry on a current collector, and drying at high temperature to remove the solvent to obtain the positive plate.
6. A lithium-sulfur battery assembled by using the positive electrode according to claim 4, comprising the positive electrode, the negative electrode, a separator for separating the positive electrode and the negative electrode, and an electrolyte for impregnating the positive electrode and the negative electrode;
the negative electrode is a metal lithium negative electrode;
the electrolyte comprises a solvent, lithium salt and an additive, wherein the solvent is DOL and DME; the lithium salt is LiTFSI; the additive is LiNO3。
7. The lithium sulfur battery of claim 6,
the positive active material has a structural formula of
Adding 0.06g of acetylene black serving as a conductive agent and 0.03g of polyvinylidene fluoride serving as a bonding agent into 0.21g of ground active material, uniformly mixing, putting the mixture into 1.8g N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, putting the copper foil into an oven with the temperature of 80 ℃ for drying, punching the mixture into a pole piece by using a punch with the diameter of 13mm, tabletting the pole piece under the pressure of 1MPa, putting the pole piece into a vacuum oven with the temperature of 100 ℃ for drying for 4 hours to obtain a positive pole piece, transferring the positive pole piece into an argon glove box, taking a metal lithium piece as a negative pole, selecting a polypropylene microporous membrane with the model of Celgard 2400 as a diaphragm, and using 1.0M LiTFSI DOL as an electrolyte, wherein DME is 1:1 (V: V) +0.2M3And assembling the cell into a CR2025 cell.
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